JP2002201152A - Method for producing fluorine-containing ether compound - Google Patents

Method for producing fluorine-containing ether compound

Info

Publication number
JP2002201152A
JP2002201152A JP2000402345A JP2000402345A JP2002201152A JP 2002201152 A JP2002201152 A JP 2002201152A JP 2000402345 A JP2000402345 A JP 2000402345A JP 2000402345 A JP2000402345 A JP 2000402345A JP 2002201152 A JP2002201152 A JP 2002201152A
Authority
JP
Grant status
Application
Patent type
Prior art keywords
fluorine
reaction
compound
solvent
containing ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000402345A
Other languages
Japanese (ja)
Other versions
JP3482488B2 (en )
Inventor
Junji Murata
Akira Sekiya
Masanori Tamura
潤治 村田
正則 田村
章 関屋
Original Assignee
National Institute Of Advanced Industrial & Technology
Research Institute Of Innovative Technology For The Earth
独立行政法人産業技術総合研究所
財団法人地球環境産業技術研究機構
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing ether, by which the by-production of an olefin compound as an impurity can be controlled and further by which the produced fluorine-containing ether compound can easily be separated from a solvent. SOLUTION: This method for producing the fluorine-containing ether is characterized by reacting an alcohol represented by formula (1): CmHnFoXpOH (1) [X is a halogen atom; (m) is an integer of 1 to 5; (n), (o) and (p) are each an integer of >=0; (n)+(o)+(p)=2(m)-1] with a fluorine-containing olefin represented by formula (2): CF2=CYZ (2) (Y and Z are each independently trifluoromethyl, fluorine atom, chlorine atom, bromine atom and hydrogen atom) in the presence of a basic compound in water solvent.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】本発明は、含フッ素エーテル化合物の製造方法に関する。 The present invention relates to a method for producing a fluorine-containing ether compound.

【0002】 [0002]

【従来の技術】従来、含フッ素エーテル化合物を得るために、アルカリ金属またはアルカリ金属水酸化物の存在下でアルコールと含フッ素オレフィン化合物とを反応させることは知られている(米国特許3557294 Conventionally, in order to obtain a fluorine-containing ether compound, reacting the alcohol with a fluorinated olefin compound in the presence of an alkali metal or alkali metal hydroxide is known (U.S. Pat. 3,557,294
号)。 issue). また有機溶媒中で反応を行うことにより穏やかな反応条件で高収率で含フッ素エーテル化合物を合成できることも知られている(特開平9−263559号)。 It is also known that can be synthesized a fluorinated ether compound in high yield under mild reaction conditions by conducting the reaction in an organic solvent (JP-A-9-263559).

【0003】上述した米国特許3557294号の方法では、原料であるアルコールを溶媒として用いて反応が行われている。 [0003] In the above-mentioned U.S. Patent 3,557,294 No. of methods, reaction with an alcohol which is a raw material as a solvent is performed. また、特開平9−263559号の方法では、有機溶媒中で反応が行われている。 Further, in JP-A 9-263559 Patent methods, in an organic solvent is performed. 有機溶媒中で反応を行う場合、反応後に生成物を溶媒から分離する必要があり、精製が困難である。 When the reaction is carried out in an organic solvent, it is necessary to separate the product from the solvent after the reaction, it is difficult to purify. しかし、これらの反応を水溶媒中で行った例はない。 However, examples are not subjected to these reactions in a water solvent. さらに本発明者らがアルコールとヘキサフルオロプロペンの反応を原料であるアルコール溶媒中、また有機溶媒中で試みたところ、中間体カルバニオンからフッ素原子が脱離したことにより生成するオレフィン化合物が副生することが分かった。 Further alcohol solvent present inventors which is a raw material of the reaction of the alcohol and hexafluoropropene, also was tried in an organic solvent, the olefin compound produced by the intermediate carbanion is fluorine atom desorbed by-produced it was found. また、いずれの方法においても副生するオレフィン化合物の沸点が目的とする含フッ素エーテルの沸点と近いために蒸留による精製は困難であることが分かった。 Further, the boiling point of the olefin compound that is also a by-product in any of the methods were found to be purified by distillation to near the boiling point of the fluorinated ether of interest is difficult.

【0004】 [0004]

【発明が解決しようとする課題】本発明は、不純物であるオレフィン化合物の副生を抑え、更に生成する含フッ素エーテル化合物の溶媒からの分離が容易な含フッ素エーテルの製造方法を提供することをその課題とする。 SUMMARY OF THE INVENTION It is an object of the present invention to suppress the by-production of olefinic compounds as impurities, to provide a method of manufacturing a easy fluorinated ether separated from the solvent of the resulting fluorine-containing ether compound and its challenges.

【0005】 [0005]

【課題を解決するための手段】本発明者らは前記課題を解決すべく鋭意研究を重ねた結果、水溶媒中で反応を行うことにより、不純物であるオレフィン化合物を生成を抑え、さらに目的とする含フッ素エーテル化合物の溶媒からの分離が容易な製造方法を見いだし、本発明の完成に至った。 The present inventors have SUMMARY OF THE INVENTION As a result of extensive studies to solve the above problems, by carrying out the reaction in aqueous medium, to suppress the generation of the olefin compound as an impurity, and further objects It separated from the solvent of the fluorine-containing ether compound that is found easy manufacturing process, thereby completing the present invention. 即ち、本発明によれば、塩基性化合物の存在下、下記一般式(1) That is, according to the present invention, the presence of a basic compound represented by the following general formula (1)

【化6】C mnop OH (1) (式中、Xはハロゲン原子を示し、mは1〜5の整数を示し、n、o及びpは0以上の整数を示すが、n+o+ Embedded image C m H n F o X p OH (1) ( wherein, X represents a halogen atom, m represents an integer of 1 to 5, n, o and p represents 0 or an integer , n + o +
pの合計は2m−1である。 The sum of p is a 2m-1. )で表されるアルコールと、下記一般式(2) An alcohol represented by), the following general formula (2)

【化7】CF 2 =CYZ (2) (式中、Y及びZはそれぞれ独立してトリフルオロメチル基、フッ素原子、塩素原子、臭素原子又は水素原子を示す)で表される含フッ素オレフィンとを水溶媒中で反応させることを特徴とする下記一般式(3) Embedded image CF 2 = CYZ (2) (wherein each Y and Z are independently a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom) and the fluorine-containing olefin represented by the following general formula which comprises reacting in an aqueous solvent (3)

【化8】C mnop OCF 2 CHYZ (3) (式中、m、n、o、p、Y及びZは前記と同じ意味を有する)で表される含フッ素エーテルの製造方法が提供される。 Embedded image C m H n F o X p OCF 2 CHYZ (3) ( wherein, m, n, o, p , Y and Z have the same meanings as defined above) Preparation of fluorine-containing ether represented by a method is provided. また、本発明によれば、塩基性化合物の存在下、下記一般式(1) Further, according to the present invention, the presence of a basic compound represented by the following general formula (1)

【化9】C mnop OH (1) (式中、Xはハロゲン原子を示し、mは1〜5の整数を示し、n、o及びpは0以上の整数を示すが、n+o+ Embedded image in C m H n F o X p OH (1) ( wherein, X represents a halogen atom, m represents an integer of 1 to 5, n, o and p represents 0 or an integer , n + o +
pの合計は2m−1である。 The sum of p is a 2m-1. )で表されるアルコールと、ヘキサフルオロプロペンとを水溶媒中で反応させることを特徴とする下記一般式(4) ) And alcohol represented by the following general formula and hexafluoropropene, wherein the reaction is carried out in an aqueous solvent (4)

【化10】 C mnop OCF 2 CHFCF 3 (4) (式中、m、n、o、pは前記と同じ意味を有する)で表される含フッ素エーテルの製造方法が提供される。 Embedded image C m H n F o X p OCF 2 CHFCF 3 (4) ( wherein, m, n, o, p has the same meaning as above) process for producing a fluorinated ether represented by the provision It is.

【0006】 [0006]

【発明の実施の形態】本発明で用いるアルコールは、前記一般式(1)で表される。 The alcohol used in the present invention DETAILED DESCRIPTION OF THE INVENTION, represented by the general formula (1). 前記一般式(1)において、Xはハロゲン原子を示すが、このハロゲン原子には、通常、塩素や臭素、フッ素が包含される。 In Formula (1), X is a halogen atom, this halogen atom, usually chlorine or bromine, fluorine and the like. 前記一般式(1)において、mは1〜5の整数、好ましくは1〜 In the general formula (1), m is an integer of 1 to 5, preferably 1 to
3の整数である。 3 of an integer. n、o及びpは0以上の整数であるが、その合計[n+o+p]は2m−1である。 n, although o and p is an integer of 0 or more, the sum [n + o + p] is 2m-1. 前記アルコールの具体例としては、例えば、CH 3 OH、C 2 Specific examples of the alcohols are, for example, CH 3 OH, C 2 H
5 OH、(CH 3 ) 2 CHOH、CF 3 CH 2 OH、CF 3 5 OH, (CH 3) 2 CHOH, CF 3 CH 2 OH, CF 3 C
2 CH 2 OH、CHF 2 CF 2 CH 2 OH、(CF 3 ) 2 CH F 2 CH 2 OH, CHF 2 CF 2 CH 2 OH, (CF 3) 2 CH
OH、CClF 2 CF 2 CH 2 CH 2 OH等が挙げられる。 OH, include CClF 2 CF 2 CH 2 CH 2 OH and the like.

【0007】本発明の他方の原料として用いる含フッ素オレフィン化合物は、前記一般式(2)で表される。 [0007] fluorine-containing olefin compound used as the other starting material of the present invention is represented by the general formula (2). 前記一般式(2)において、Y及びZは、それぞれ独立して、トリフルオロメチル基(CF 3 )、フッ素原子、塩素原子又は水素原子を示す。 In the formula (2), Y and Z are each independently a trifluoromethyl group (CF 3), a fluorine atom, a chlorine atom or a hydrogen atom. 前記含フッ素オレフィン化合物の具体例としては、例えば、CF 2 =CF 2 、CF 2 Specific examples of the fluorine-containing olefin compound, e.g., CF 2 = CF 2, CF 2
=CH 2 、CF 2 =CHF、CF 2 =CBr 2 、CF 2 =C = CH 2, CF 2 = CHF , CF 2 = CBr 2, CF 2 = C
FCl、CF 2 =CFCF 3等が挙げられる。 FCl, CF 2 = CFCF 3, and the like. 本発明では、好ましくは、ヘキサフルオロプロペンが用いられる。 In the present invention, preferably, hexafluoropropene is used.

【0008】本発明により含フッ素エーテルを製造するには、前記アルコールを塩基性化合物の存在下及び水溶媒体中で、前記含フッ素オレフィン化合物と反応させる。 [0008] To produce the fluorinated ether by the present invention, the alcohol through the presence and water medium of a basic compound is reacted with the fluorine-containing olefin compound. 塩基性化合物としては、無機塩基及び有機塩基のいずれもを使用することができる。 The basic compound can be used any of inorganic bases and organic bases. 無機塩基には、NaO The inorganic base, NaO
H、KOH、NaH等の塩基性アルカリ金属化合物や、 H, KOH, or a basic alkali metal compound such as NaH,
Ca(OH) 2 、CaH 2等の塩基性アルカリ土類金属化合物が包含される。 Ca (OH) 2, CaH basic alkaline earth metal compound such as 2 and the like. 有機塩基には、第1級、第2級及び第3級有機アミンが包含される。 Organic bases, primary, secondary and tertiary organic amines, and the like. 有機アミンにおいて、その沸点は0〜120℃、好ましくは20〜100℃である。 In the organic amine, its boiling point is 0 to 120 ° C., preferably from 20 to 100 ° C.. 本発明では、特に、第3級アミン、例えば、(CH In the present invention, in particular, tertiary amines, e.g., (CH
3 CH 2 ) 3 N等の炭素数1〜10、好ましくは1〜6のアルキル基を有するトリアルキルアミンの使用が好ましい。 3 CH 2) 3 N carbon atoms such as 1 to 10, preferably using a trialkylamine having from 1 to 6 alkyl groups. 塩基性化合物の使用割合は、特に制約されないが、 The ratio of the basic compound is not particularly limited,
原料アルコール1モル当り、0.01当量以上、好ましくは0.1当量以上である。 Starting alcohol per mole, 0.01 equivalent or more, preferably 0.1 equivalent or more. その上限値は、通常10当量程度である。 Its upper limit is usually 10 equivalents. 塩基性化合物の割合が少なすぎると、反応が効率よく進行しない。 When the ratio of the basic compound is too small, the reaction does not proceed efficiently. 一方、多すぎると副反応が起しやすくなる。 On the other hand, too large a side reaction becomes prone.

【0009】本発明で用いる含フッ素オレフィン化合物は常温でガス状のものであり、その反応に際しての圧力は特に限定されないが、あまりに高圧下で行っても含フッ素オレフィン化合物の重合反応が併発する、装置的に高価になる、などの問題が生じるため、30kgf/c [0009] fluorine-containing olefin compound used in the present invention are those gaseous at normal temperature, but the pressure is not particularly limited in the time that reaction, comorbid polymerization reaction be carried out under too high pressure fluorine-containing olefin compound, since the apparatus specifically be expensive, such problems arise, 30 kgf / c
2以下が好ましく、より好ましくは20kgf/cm 2 m 2 or less, more preferably 20 kgf / cm 2
以下である。 Less. その下限値は、通常、5kg/cm 2程度である。 The lower limit is usually, 5 kg / cm 2 approximately. 含フッ素オレフィンは全量を反応初期に仕込むことも、反応中に連続的または間欠的に供給することも可能である。 Fluorine-containing olefins be charged the total amount in the reaction initial stage, it is also possible to continuously or intermittently supplied into the reaction.

【0010】本発明における最大の効果は反応を水溶媒中で行うことにより達成される。 Maximum effect in [0010] The present invention is achieved by carrying out the reaction in a water solvent. 溶媒として用いる水は、水道水でも構わず、特に制限されないが、イオン交換水、蒸留水を用いた方が、不純物の混入が少なく好ましい。 Used as a solvent water is not may be tap water, it is not particularly limited, ion exchange water, preferable to use distilled water, contamination of impurities is less preferred. また、水の他に水溶性有機溶媒を添加しても構わないが、反応生成物の精製が困難になるために添加しない方が好ましい。 Although it may be added in addition to water-soluble organic solvent of water, it is preferable that the purification of the reaction product not added to become difficult. このような有機溶媒としては、特に限定はされないが、ジエチルエーテル、グライム類、ジオキサン、テトラヒドロフラン、アセトニトリルを挙げることができる。 Examples of such an organic solvent is not particularly limited, it may be mentioned diethyl ether, glymes, dioxane, tetrahydrofuran, acetonitrile. また、反応原料と水との相溶性を向上するために界面活性剤類を添加しても構わない。 Also, it may be added to surfactants in order to improve the compatibility of the reactants and the water. 有機溶媒を含む水溶媒を用いる場合、その有機溶媒の濃度は20 When using a water solvent containing an organic solvent, concentration of the organic solvent 20
%以下、好ましくは10%以下である。 % Or less, preferably 10% or less. 本発明で溶媒として用いる水の使用量は特に限定されないが、好ましくは原料のアルコールに対して重量で100倍以下、より好ましくは50倍以下である。 The amount of water used as a solvent in the present invention is not particularly limited, but is preferably 100 times or less by weight with respect to the alcohol feedstock, more preferably not more than 50 times. その下限値は、通常5倍程度である。 The lower limit is usually 5 times. 本発明における反応の温度は特に限定されるものではないが、あまりに高すぎる場合は副反応が起こり、あまりに低すぎる場合は反応が進行しないため、 Since there are no particular limitation temperature of the reaction in the present invention, occur too if too high side reaction, not the reaction proceeds if too low,
反応速度に応じて反応温度を選べば良い。 It may be selected reaction temperature depending on the reaction rate. 一般的には1 In general, 1
0〜120℃の範囲であり、好ましくは50〜100℃ In the range of 0 to 120 ° C., preferably from 50 to 100 ° C.
の範囲である。 It is in the range of.

【0011】本発明の反応は次式で表される。 [0011] The reaction of the present invention is represented by the following formula. op OH+CH 2 =CYZ→ C op OCF 2 CHYZ (5) 前記反応における原料の導入方法は特に限定されないが、あらかじめ、水、アルコール、塩基性化合物を一緒に導入しておき、含フッ素オレフィンを導入する方法が一般的である。 Although C m H n F o X p OH + CH 2 = CYZ → C m H n F o X p OCF 2 CHYZ (5) a method for introducing the raw material in the reaction is not particularly limited, advance, water, alcohol, a basic compound together previously introduced a method of introducing a fluorine-containing olefin are common. なお、本発明において反応生成物の含フッ素エーテル化合物は水に対してほとんど溶解しないため、反応終了時には溶媒である水と含フッ素エーテル化合物は相分離しており、下層を抜き出すだけで容易に溶媒である水からの分離が可能である。 Since the fluorine-containing ether compound of the reaction products in the present invention is hardly soluble in water, water and fluorine-containing ether compound at the end of the reaction the solvent is phase separated, readily solvent just extracting the lower it can be separated from the water is. また、下層を抜き出した後に、原料であるアルコールを添加して改めて含フッ素オレフィン化合物を導入することにより続けて反応を行うことが可能である。 Further, after extracting the lower layer, the reaction can be carried out to continue by introducing again the fluorine-containing olefin compound with the addition of alcohol as a raw material. 続けて反応を行う場合、適宜、水や塩基性化合物を補充しても何ら問題ない。 When the reaction is carried out continuously, as appropriate, no problem even if supplemented with water or a basic compound. また、本発明では、副生物であるオレフィン化合物の生成を抑えることができる。 In the present invention, it is possible to suppress the generation of olefinic compounds by-product. これはアルコキシドと含フッ素オレフィンの付加反応により生成する中間体カルバニオンが、溶媒である水のプロトンと速やかに反応するためであると考えられる。 This intermediate carbanion produced by addition reaction of alkoxide with fluorine-containing olefin is believed to be to react rapidly with water protons as a solvent. 本発明の製造例を実施例を挙げて説明する。 It will be described by way of production examples of the present invention embodiment. もちろん、本発明は以下の例によって限定されるものではない。 Of course, the invention is not limited by the following examples.

【0012】 [0012]

【実施例】次に本発明を実施例及び比較例を挙げて詳述する。 EXAMPLE now be described in detail by way of the present invention examples and comparative examples.

【0013】比較例1 内容量25mlのステンレス製圧力反応器に、2,2, [0013] Into a stainless steel pressure reactor of Comparative Example 1 Contents 25 ml, 2, 2,
2−トリフルオロエタノール3.03gと水酸化カリウム168mgを仕込んだ。 They were charged 2-trifluoroethanol 3.03g of potassium hydroxide 168 mg. 液体窒素で反応容器を冷やしながら系内を脱気した後、真空ラインを用いてヘキサフルオロプロパン1.50gを仕込んだ。 After degassing the inside of the system while cooling the reaction vessel in liquid nitrogen and charged with hexafluoropropane 1.50g using a vacuum line. 反応器を25℃ The reactor 25 ° C.
に保ち24時間攪拌した。 The mixture was stirred for 24 hours kept to. 反応により得られた粗生成物を1 H−NMR、 19 F−NMRで測定した結果、NMR Results The crude product obtained by the reaction was measured by 1 H-NMR, 19 F- NMR, NMR
面積比で目的とする1,1,2,3,3,3−ヘキサフルオロ−1−(2,2,2−トリフルオロエトキシ)プロパン2.23g(収率89%)と副生成物である1, Is-products to the desired 1,1,2,3,3,3-hexafluoro-1- (2,2,2-trifluoroethoxy) propane 2.23 g (89% yield) of an area ratio 1,
2,3,3,3−ペンタフルオロ−1−(2,2,2− 2,3,3,3-penta-fluoro-1- (2,2,2
トリフルオロエトキシ)−1−プロペン0.232g Trifluoroethoxy) -1-propene 0.232g
(収率10%)を得た。 Was obtained (10% yield).

【0014】比較例2 内容量25mlのステンレス製圧力反応器に2,2, [0014] Into a stainless steel pressure reactor of Comparative Example 2 Contents 25 ml 2, 2,
3,3,3−ペンタフルオロプロパノール4.51gと水酸化カリウム168mgを仕込んだ。 It was charged 3,3,3-pentafluoro-propanol 4.51g of potassium hydroxide 168 mg. 液体窒素で反応容器を冷やしながら系内を脱気した後、真空ラインを用いてヘキサフルオロプロパン1.50gを仕込んだ。 After degassing the inside of the system while cooling the reaction vessel in liquid nitrogen and charged with hexafluoropropane 1.50g using a vacuum line. 反応器を25℃に保ち24時間攪拌した。 The reactor was stirred for 24 hours maintained at 25 ° C.. 反応により得られた粗生成物を1 H−NMR、 19 F−NMRで測定した結果、NMR面積比で目的とする1,1,2,3,3, The crude product obtained by reacting 1 H-NMR, 19 result measured by F-NMR, 1,1,2,3,3 of interest in NMR area ratio,
3−ヘキサフルオロ−1−(2,2,3,3,3−ペンタフルオロプロポキシ)プロパン2.53g(収率84 3-hexafluoro-1- (2,2,3,3,3-pentafluoropropoxy) propane 2.53 g (yield: 84
%)と副生成物である1,2,3,3,3−ペンタフルオロ−1−(2,2,3,3,3−ペンタフルオロプロポキシ)−1−プロペン0.391g(収率14%)を得た。 %) As a by-product 1,2,3,3,3-pentafluoro-1- (2,2,3,3,3-pentafluoropropoxy) 1-propene 0.391 g (yield: 14% ) was obtained.

【0015】比較例3 内容量25mlのステンレス製圧力反応器に2,2, [0015] Into a stainless steel pressure reactor of Comparative Example 3 Contents 25 ml 2, 2,
3,3−テトラフルオロプロパノール3.96gと水酸化カリウム169mgを仕込んだ。 They were charged 3,3-tetrafluoropropanol 3.96g of potassium hydroxide 169 mg. 液体窒素で反応容器を冷やしながら系内を脱気した後、真空ラインを用いてヘキサフルオロプロパン1.50gを仕込んだ。 After degassing the inside of the system while cooling the reaction vessel in liquid nitrogen and charged with hexafluoropropane 1.50g using a vacuum line. 反応器を25℃に保ち24時間攪拌した。 The reactor was stirred for 24 hours maintained at 25 ° C.. 反応により得られた粗生成物を1 H−NMR、 19 F−NMRで測定した結果、NMR面積比で目的とする1,1,2,3,3,3 The reaction results obtained crude product was measured by 1 H-NMR, 19 F- NMR , the aims by NMR area ratio 1,1,2,3,3,3
−ヘキサフルオロ−1−(2,2,3,3−テトラフルオロプロポキシ)プロパン2.52g(収率89%)と副生成物である1,2,3,3,3−ペンタフルオロ− - hexafluoro-1- (2,2,3,3-tetrafluoro-propoxy) is a by-product propane 2.52 g (89% yield) of 1,2,3,3,3-pentafluoro -
1−(2,2,3,3−テトラフルオロプロポキシ)− 1- (2,2,3,3-tetrafluoro-propoxy) -
1−プロペン0.293g(収率11%)を得た。 To give 1-propene 0.293g (11% yield).

【0016】比較例4 内容量25mlのステンレス製圧力反応器に2,2,2 [0016] Into a stainless steel pressure reactor of Comparative Example 4 Contents 25 ml 2,2,2
−トリフルオロエタノール1.12gと水酸化カリウム168mgと1,4−ジオキサン5mlを仕込んだ。 - it was charged trifluoroethanol 1.12g and potassium hydroxide 168mg and 1,4-dioxane 5 ml. 液体窒素で反応容器を冷やしながら系内を脱気した後、真空ラインを用いてヘキサフルオロプロパン1.5gを仕込んだ。 After degassing the inside of the system while cooling the reaction vessel in liquid nitrogen and charged with hexafluoropropane 1.5g using a vacuum line. 反応器を25℃で24時間攪拌した。 The reactor was stirred for 24 hours at 25 ° C.. 反応により得られた粗生成物を1 H−NMR、 19 F−NMRで測定した結果、NMR面積比で目的とする1,1,2, The crude product obtained by reacting 1 H-NMR, 19 result measured by F-NMR, 1, 1, 2 of interest in NMR area ratio,
3,3,3−ヘキサフルオロ−1−(2,2,2−トリフルオロエトキシ)プロパン1.72g(収率69%) 3,3,3-hexafluoro-1- (2,2,2-trifluoroethoxy) propane 1.72 g (69% yield)
と副生成物である1,2,3,3,3−ペンタフルオロ−1−(2,2,2−トリフルオロエトキシ)−1−プロペン0.463g(収率20%)を得た。 A by-product 1,2,3,3,3-pentafluoro-1- (2,2,2-trifluoroethoxy) -1-propene 0.463 g (20% yield).

【0017】実施例1 内容量200mlのステンレス製圧力反応器に2,2, [0017] Into a stainless steel pressure reactor of Example 1 Contents 200 ml 2, 2,
2−トリフルオロエタノール10.0gと水酸化カリウム5.61gとイオン交換水50mlを仕込んだ。 They were charged 2-trifluoroethanol 10.0g of potassium hydroxide 5.61g of deionized water 50 ml. 液体窒素で反応器を冷やしながら系内を脱気した後、室温に戻しヘキサフルオロプロペンで0.5Mpaまで加圧した。 After degassing the inside of the system while cooling the reactor with liquid nitrogen, pressurized to 0.5Mpa with hexafluoropropene returned to room temperature. ヘキサフルオロプロペンの圧力を約0.5Mpaに保ったまま、反応器を75℃まで昇温し24時間攪拌した。 While maintaining the pressure of hexafluoropropene to about 0.5Mpa, the reactor was stirred heated 24 hours 75 ° C.. 反応後、二層分離した下層を抜き出し、得られた粗生成物を1 H−NMR、 19 F−NMRで分析した結果、 After the reaction, extracting the lower layer was separated into two layers, the resulting crude product was analyzed by 1 H-NMR, 19 F- NMR results,
目的とする1,1,2,3,3,3−ヘキサフルオロ− For the purpose 1,1,2,3,3,3-hexafluoro -
1−(2,2,2−トリフルオロエトキシ)プロパン2 1- (2,2,2-trifluoroethoxy) propane 2
4.1g(収率96%)を得た。 It was obtained 4.1 g (96% yield). また19 F−NMRから粗生成物中に副生成物である1,2,3,3,3−ペンタフルオロ−1−(2,2,2−トリフルオロエトキシ)−1−プロペンは認められなかった。 Also in the crude product from 19 F-NMR as a by-product 1,2,3,3,3-pentafluoro-1- (2,2,2-trifluoroethoxy) -1-propene observed It was.

【0018】実施例2 内容量200mlのステンレス製圧力反応器に2,2, [0018] Into a stainless steel pressure reactor of Example 2 Contents 200 ml 2, 2,
3,3,3−ペンタフルオロプロパノール15.0gと水酸化カリウム5.61gとイオン交換水50mlを仕込んだ。 It was charged 3,3,3-pentafluoro-propanol 15.0g of potassium hydroxide 5.61g of deionized water 50 ml. 液体窒素で反応器を冷やしながら系内を脱気した後、室温に戻しヘキサフルオロプロペンで0.5Mp After degassing the inside of the system while cooling the reactor with liquid nitrogen, 0.5 MPa at hexafluoropropene returned to room temperature
aまで加圧した。 Pressurized to a. ヘキサフルオロプロペンの圧力を約0.5Mpaに保ったまま、反応器を75℃まで昇温し24時間攪拌した。 While maintaining the pressure of hexafluoropropene to about 0.5Mpa, the reactor was stirred heated 24 hours 75 ° C.. 反応後、二層分離した下層を抜き出し、得られた粗生成物を1 H−NMR、 19 F−NMRで測定した結果、NMR面積比で目的とする1,1,2, After the reaction, extracting the lower layer was separated into two layers, the results of the obtained crude product was measured by 1 H-NMR, 19 F- NMR, 1,1,2 of interest by NMR area ratio,
3,3,3−ヘキサフルオロ−1−(2,2,3,3, 3,3,3-hexafluoro-1- (2, 2, 3, 3,
3−ペンタフルオロプロポキシ)プロパン28.3g 3-pentafluoro propoxy) propane 28.3g
(収率95%)と副生成物である1,2,3,3,3− (95% yield) as a by-product 1,2,3,3,3
ペンタフルオロ−1−(2,2,3,3,3−ペンタフルオロプロポキシ)−1−プロペン0.60g(収率2 Pentafluoro-1- (2,2,3,3,3-pentafluoropropoxy) 1-propene 0.60 g (yield: 2
%)を得た。 %) Was obtained.

【0019】実施例3 内容量200mlのステンレス製圧力反応器に2,2, The stainless steel pressure reactor of Example 3 Contents 200 ml 2, 2,
3,3−テトラフルオロプロパノール13.2gと水酸化カリウム5.61gとイオン交換水50mlを仕込んだ。 They were charged 3,3-tetrafluoropropanol 13.2g of potassium hydroxide 5.61g of deionized water 50 ml. 液体窒素で反応器を冷やしながら系内を脱気した後、室温に戻しヘキサフルオロプロペンで0.5Mpa After degassing the inside of the system while cooling the reactor with liquid nitrogen, 0.5Mpa with hexafluoropropene returned to room temperature
まで加圧した。 Until it pressurized. ヘキサフルオロプロペンの圧力を約0. The pressure of the hexafluoropropene about 0.
5Mpaに保ったまま、反応器を75℃まで昇温し24 While maintaining the 5 Mpa, heated reactor to 75 ° C. 24
時間攪拌した。 Time and the mixture was stirred. 反応後、二層分離した下層を抜き出し、 After the reaction, extracting the lower layer was separated into two layers,
得られた粗生成物を1 H−NMR、 1 9 F−NMRで測定した結果、NMR面積比で目的とする1,1,2,3, Results The obtained crude product was measured by 1 H-NMR, 1 9 F -NMR, 1,1,2,3 of interest in NMR area ratio,
3,3−ヘキサフルオロ−1−(2,2,3,3−テトラフルオロプロポキシ)プロパン27.5g(収率97 3,3-hexafluoro-1- (2,2,3,3-tetrafluoro-propoxy) propane 27.5 g (yield: 97
%)と副生成物である1,2,3,3,3−ペンタフルオロ−1−(2,2,3,3−テトラフルオロプロポキシ)−1−プロペン0.51g(収率2%)を得た。 %) As a by-product 1,2,3,3,3-pentafluoro-1- (2,2,3,3-tetrafluoro-propoxy) -1-propene 0.51g (2% yield) Obtained.

【0020】次に、前記アルコールとヘキサフルオロプロペンとの反応の結果を次表にまとめて示す。 [0020] Next, the result of reaction between the alcohol and hexafluoropropene are summarized in the following table.

【0021】 [0021]

【表1】 [Table 1]

【0022】実施例4 内容量200mlのステンレス製圧力反応器に2,2, The stainless steel pressure reactor of Example 4 Contents 200 ml 2, 2,
3,3,3−ペンタフルオロプロパノール15.0gと水酸化カリウム11.2gとイオン交換水50mlを仕込んだ。 It was charged 3,3,3-pentafluoro-propanol 15.0g of potassium hydroxide 11.2g of deionized water 50 ml. 液体窒素で反応器を冷やしながら系内を脱気した後、室温に戻しヘキサフルオロプロペンで0.5Mp After degassing the inside of the system while cooling the reactor with liquid nitrogen, 0.5 MPa at hexafluoropropene returned to room temperature
aまで加圧した。 Pressurized to a. ヘキサフルオロプロペンの圧力を約0.5Mpaに保ったまま、反応器を80℃まで昇温し24時間攪拌した。 While maintaining the pressure of hexafluoropropene to about 0.5Mpa, the reactor was stirred heated 24 hours 80 ° C.. 反応後、二層分離した下層を抜き出し、得られた粗生成物を1 H−NMR、 19 F−NMRで測定した結果、NMR面積比で目的とする2,2,3, After the reaction, extracting the lower layer was separated into two layers, the results of the obtained crude product was measured by 1 H-NMR, 19 F- NMR, 2,2,3 of interest by NMR area ratio,
3,3−ペンタフルオロ−1−(1,1,2,2−テトラフルオロエトキシ)プロパン15.1g(収率60 3,3-pentafluoro-1- (1,1,2,2-tetrafluoroethoxy) propane 15.1 g (yield: 60
%)を得た。 %) Was obtained.

【0023】 [0023]

【発明の効果】本発明によれば、塩基性条件下、アルコールと含フッ素オレフィン化合物の反応を水溶媒中で行うことにより、副生成物であるオレフィン化合物の生成を抑え、反応後の分離が容易な含フッ素エーテル化合物の製造が可能である。 According to the present invention, under basic conditions, by carrying out the reaction of the alcohol with the fluorinated olefin compound in an aqueous solvent in suppresses the production of olefinic compounds as a by-product, is separated after the reaction it is possible to produce easy fluorinated ether compound.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 村田 潤治 東京都文京区本郷2−40−17本郷若井ビル 6階 財団法人地球環境産業技術研究機構 新規冷媒等プロジェクト室内 (72)発明者 関屋 章 茨城県つくば市東1丁目1番 工業技術院 物質工学工業技術研究所内 (72)発明者 田村 正則 茨城県つくば市東1丁目1番 工業技術院 物質工学工業技術研究所内 Fターム(参考) 4H006 AA02 AC21 AC30 AC43 BA02 BA06 BA28 BA29 BA69 GN35 GP01 4H039 CA50 CA61 CF10 ────────────────────────────────────────────────── ─── of the front page continued (72) inventor Murata Junji Hongo, Bunkyo-ku, Tokyo 2-40-17 Hongo Wakai building sixth floor research Institute of Innovative technology for the Earth new refrigerant such as a project room (72) inventor Akira Sekiya Ibaraki prefecture Higashi, Tsukuba, 1 chome Agency substance of industrial Science and technology in the Laboratory (72) inventor Masanori Tamura Higashi, Tsukuba, Ibaraki 1 chome Agency substance Institute of Advanced industrial Science and technology in the F-term (reference) 4H006 AA02 AC21 AC30 AC43 BA02 BA06 BA28 BA29 BA69 GN35 GP01 4H039 CA50 CA61 CF10

Claims (2)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 塩基性化合物の存在下、下記一般式(1) 【化1】C mnop OH (1) (式中、Xはハロゲン原子を示し、mは1〜5の整数を示し、n、o及びpは0以上の整数を示すが、n+o+ Presence of claim 1 wherein the base compound represented by the following general formula (1) ## STR1 C m H n F o X p OH (1) ( wherein, X represents a halogen atom, m is 1 to 5 of an integer, n, o and p represents 0 or an integer, n + o +
    pの合計は2m−1である。 The sum of p is a 2m-1. )で表されるアルコールと、下記一般式(2) 【化2】CF 2 =CYZ (2) (式中、Y及びZはそれぞれ独立してトリフルオロメチル基、フッ素原子、塩素原子、臭素原子又は水素原子を示す)で表される含フッ素オレフィンとを水溶媒中で反応させることを特徴とする下記一般式(3) 【化3】C mnop OCF 2 CHYZ (3) (式中、m、n、o、p、Y及びZは前記と同じ意味を有する)で表される含フッ素エーテルの製造方法。 ) And alcohol represented by the following general formula (2) ## STR2 ## CF 2 = CYZ (2) (wherein, trifluoromethyl groups Y and Z are each independently a fluorine atom, a chlorine atom, a bromine atom or the following general formula and a fluorine-containing olefin comprising reacting in an aqueous solvent represented by hydrogen atoms showing a) (3) ## STR3 ## C m H n F o X p OCF 2 CHYZ (3) (wherein, m, n, o, p, Y and Z have the same meanings as defined above) process for producing a fluorinated ether represented by.
  2. 【請求項2】 塩基性化合物の存在下、下記一般式(1) 【化4】C mnop OH (1) (式中、Xはハロゲン原子を示し、mは1〜5の整数を示し、n、o及びpは0以上の整数を示すが、n+o+ The presence of 2. A basic compound represented by the following general formula (1) ## STR4 C m H n F o X p OH (1) ( wherein, X represents a halogen atom, m is 1 to 5 of an integer, n, o and p represents 0 or an integer, n + o +
    pの合計は2m−1である。 The sum of p is a 2m-1. )で表されるアルコールと、ヘキサフルオロプロペンとを水溶媒中で反応させることを特徴とする下記一般式(4) 【化5】C mnop OCF 2 CHFCF 3 (4) (式中、m、n、o、pは前記と同じ意味を有する)で表される含フッ素エーテルの製造方法。 ) And alcohol represented by the following general formula and hexafluoropropene, wherein the reaction is carried out in an aqueous solvent (4) embedded image C m H n F o X p OCF 2 CHFCF 3 (4) ( wherein, m, n, o, p is process for producing a fluorinated ether represented by have) as defined above.
JP2000402345A 2000-12-28 2000-12-28 Process for producing a fluorinated ether compound Active JP3482488B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000402345A JP3482488B2 (en) 2000-12-28 2000-12-28 Process for producing a fluorinated ether compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2000402345A JP3482488B2 (en) 2000-12-28 2000-12-28 Process for producing a fluorinated ether compound

Publications (2)

Publication Number Publication Date
JP2002201152A true true JP2002201152A (en) 2002-07-16
JP3482488B2 JP3482488B2 (en) 2003-12-22

Family

ID=18866666

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2000402345A Active JP3482488B2 (en) 2000-12-28 2000-12-28 Process for producing a fluorinated ether compound

Country Status (1)

Country Link
JP (1) JP3482488B2 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292452A (en) * 2003-03-27 2004-10-21 Solvay Solexis Spa Method for producing hydrofluoroethers
WO2004108644A1 (en) * 2003-06-04 2004-12-16 Asahi Glass Company, Limited Method for producing fluorine-containing alkyl ether
JP2005213255A (en) * 2004-01-29 2005-08-11 Solvay Solexis Spa Method for producing fluorohalogen ether
JP2005213256A (en) * 2004-01-29 2005-08-11 Solvay Solexis Spa Method for producing fluorohalogen ether
WO2006123563A1 (en) * 2005-05-17 2006-11-23 Asahi Glass Company, Limited Method for processing fluorinated alkyl ether
JP2008230981A (en) * 2007-03-16 2008-10-02 Daikin Ind Ltd Method for producing highly pure fluorine-containing alkyl ether
JP2009507840A (en) * 2005-09-08 2009-02-26 スリーエム イノベイティブ プロパティズ カンパニー Hydrofluoroether compounds and their preparation and use
WO2009154135A1 (en) 2008-06-20 2009-12-23 ダイキン工業株式会社 Method for producing fluorine-containing ether
US7790312B2 (en) 2005-09-08 2010-09-07 3M Innovative Properties Company Electrolyte composition
WO2010147105A1 (en) 2009-06-15 2010-12-23 ダイキン工業株式会社 Method for producing fluorine-containing ether with high purity
JP4640175B2 (en) * 2003-08-11 2011-03-02 旭硝子株式会社 Process for producing a fluorinated alkyl ether
CN103254041A (en) * 2013-05-03 2013-08-21 巨化集团技术中心 Preparation method of hydrofluoroether
US9842993B2 (en) 2013-07-19 2017-12-12 Central Glass Company, Limited Film-forming composition, film formed thereby, and method for manufacturing organic semiconductor element using same
US9966575B2 (en) 2013-07-19 2018-05-08 Central Glass Company, Limited Composition for forming films, film produced from said composition, and method for producing organic semiconductor element using said composition

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292452A (en) * 2003-03-27 2004-10-21 Solvay Solexis Spa Method for producing hydrofluoroethers
JP4550458B2 (en) * 2003-03-27 2010-09-22 ソルヴェイ ソレクシス エス.ピー.エー.Solvay Solexis S.p.A. Preparation of hydrofluoroether
US7193118B2 (en) 2003-06-04 2007-03-20 Asahi Glass Company, Limited Method for producing fluoroalkyl ether
WO2004108644A1 (en) * 2003-06-04 2004-12-16 Asahi Glass Company, Limited Method for producing fluorine-containing alkyl ether
JP4635871B2 (en) * 2003-06-04 2011-02-23 旭硝子株式会社 Process for producing a fluorinated alkyl ether
JP4640175B2 (en) * 2003-08-11 2011-03-02 旭硝子株式会社 Process for producing a fluorinated alkyl ether
JP2005213255A (en) * 2004-01-29 2005-08-11 Solvay Solexis Spa Method for producing fluorohalogen ether
JP2005213256A (en) * 2004-01-29 2005-08-11 Solvay Solexis Spa Method for producing fluorohalogen ether
WO2006123563A1 (en) * 2005-05-17 2006-11-23 Asahi Glass Company, Limited Method for processing fluorinated alkyl ether
KR101298324B1 (en) * 2005-09-08 2013-08-20 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Hydrofluoroether compounds and processes for their preparation and use
US7691282B2 (en) 2005-09-08 2010-04-06 3M Innovative Properties Company Hydrofluoroether compounds and processes for their preparation and use
US7790312B2 (en) 2005-09-08 2010-09-07 3M Innovative Properties Company Electrolyte composition
JP2009507840A (en) * 2005-09-08 2009-02-26 スリーエム イノベイティブ プロパティズ カンパニー Hydrofluoroether compounds and their preparation and use
JP2008230981A (en) * 2007-03-16 2008-10-02 Daikin Ind Ltd Method for producing highly pure fluorine-containing alkyl ether
WO2009154135A1 (en) 2008-06-20 2009-12-23 ダイキン工業株式会社 Method for producing fluorine-containing ether
US8835696B2 (en) 2008-06-20 2014-09-16 Daikin Industries, Ltd. Method of preparing fluorine-containing ether
WO2010147105A1 (en) 2009-06-15 2010-12-23 ダイキン工業株式会社 Method for producing fluorine-containing ether with high purity
RU2486170C1 (en) * 2009-06-15 2013-06-27 Дайкин Индастриз, Лтд. Method of producing fluorine-containing ether of high purity
CN102803191B (en) * 2009-06-15 2014-11-05 大金工业株式会社 Method for producing fluorine-containing ether with high purity
CN102803191A (en) * 2009-06-15 2012-11-28 大金工业株式会社 Method for producing fluorine-containing ether with high purity
CN103254041A (en) * 2013-05-03 2013-08-21 巨化集团技术中心 Preparation method of hydrofluoroether
CN103254041B (en) * 2013-05-03 2016-04-13 巨化集团技术中心 One kind of production method hydrofluoroether
US9842993B2 (en) 2013-07-19 2017-12-12 Central Glass Company, Limited Film-forming composition, film formed thereby, and method for manufacturing organic semiconductor element using same
US9966575B2 (en) 2013-07-19 2018-05-08 Central Glass Company, Limited Composition for forming films, film produced from said composition, and method for producing organic semiconductor element using said composition

Also Published As

Publication number Publication date Type
JP3482488B2 (en) 2003-12-22 grant

Similar Documents

Publication Publication Date Title
Takaoka et al. F-propene-dialkylamine reaction products as fluorinating agents
US5382704A (en) Fluorinated methyl ethers
WO2007105633A1 (en) Polyfluoroalkyl alcohol or (meth)acrylic acid derivative thereof, and their production methods
US4736045A (en) Process for fluorinating ethers
US4515989A (en) Preparation decarboxylation and polymerization of novel acid flourides and resulting monomers
WO2002044138A1 (en) Process for producing fluorosulfonyl fluoride compound
US4687821A (en) Preparation, decarboxylation and polymerization of novel acid fluorides and resulting monomers
US6573411B2 (en) Process for the preparation of fluoropolyoxyalkylenes having one end group -CH2OH and the other end group containing chlorine
US20050288528A1 (en) Fluorinated adamantane and its derivatives
US5352785A (en) Continuous process for purifying perfluorochemical compositions
US6054626A (en) Synthesis of fluorinated ethers
WO2002055471A1 (en) Processes for producing fluorinated ester, fluorinated acyl fluoride, and fluorinated vinyl ether
US4654448A (en) Process for the synthesis of hexafluorobutadiene and of higher perfluorinated dienes
US2224849A (en) Process and products relating to glycidols
US20070203368A1 (en) Process for preparing fluorohalogenethers
JPH06192154A (en) Production of fluorine-containing ether compound
WO2002026688A1 (en) Process for producing fluorinated ester compound
US20070004938A1 (en) Method of making fluorinated vinyl ethers
CN101796002A (en) Process for producing 2,3,3,3-tetrafluoropropene
JPH09263559A (en) Production of fluorine-containing alkyl ether
WO2002026687A1 (en) Processes for the preparation of perfluoro compounds and derivatives thereof
JP2004018429A (en) Method for manufacturing fluorine-containing fluorosulfonylalkyl vinyl ether
JP2007039376A (en) Method for producing hydrofluoroether (hfe)
JP2002201152A (en) Method for producing fluorine-containing ether compound
US6747174B2 (en) Processes for the preparation of fluorinated acyl fluorides and fluorinated vinyl ethers

Legal Events

Date Code Title Description
R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20071017

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20081017

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20081017

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20091017

Year of fee payment: 6

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20091017

Year of fee payment: 6

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20091017

Year of fee payment: 6

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20091017

Year of fee payment: 6

R370 Written measure of declining of transfer procedure

Free format text: JAPANESE INTERMEDIATE CODE: R370

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20091017

Year of fee payment: 6

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101017

Year of fee payment: 7

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101017

Year of fee payment: 7

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313117

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101017

Year of fee payment: 7

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111017

Year of fee payment: 8

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111017

Year of fee payment: 8

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121017

Year of fee payment: 9

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121017

Year of fee payment: 9

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20131017

Year of fee payment: 10

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250